Modelling the role of humic acid in radiocaesium distribution in a British upland peat soil

The significance of exchange sites on organic matter in the retention of radiocaesium in highly organic soils remains unclear. To quantify this retention, we measured the binding of 134Cs to a humic acid isolated from a British upland peat soil, under a range of chemical conditions. We interpreted our results using Humic Ion Binding Model V, a model of humic substance chemistry which simulates ion exchange by non-specific accumulation of cations adjacent to the humic molecules. Model V could simulate the humic acid-solution partitioning of Cs under all the solution conditions used. The model was used to estimate the contribution of organic matter to Cs sorption by the whole soil composite. An estimate of Cs sorption by illite frayed edge sites was also made. These simulations show that organic matter may play only a minor role in binding Cs. even in highly organic soils.     

Possible role of organic matter in radiocaesium adsorption in soils

The aim of this review is to examine the hypothesis that organic matter decreases the adsorption of radiocaesium on clay minerals. The factors that determine radiocaesium mobility and bioavailability in soil are briefly outlined to show why a relationship between soil organic matter content and enhanced Cs bioavailability is paradoxical. In all the investigations reviewed the ionic compositions of both the solid and the solution phases have been strictly controlled. We show that the addition of organic matter to reference clay minerals causes decreases of up to an order of magnitude in the distribution coefficient of radiocaesium. Similarly, the chemical removal of organic matter from the clay-sized fraction of soil usually leads to an increase in Cs adsorption. We suggest that the nature of the organic matter and its interaction with mineral surfaces are as important as the amount present.     

Role of the fungal mycelium in the retention of radiocaesium in forest soils

The aim of this work was to study possible binding of 137Cs to various organic components in the soil and fungi, by using various sequential extraction procedures. The retention and binding of 137Cs has been studied in two horizons Of/Oh and Ah/B of a Ukrainian forest soil. The exchangeable fractions 137Cs from soil (sum of H2O and 1 M NH4OAc fraction) were found to be 12% in the organic-rich layer (range 11-14%) and 23% in the organic-poor (range 20-29%). The hydrolysis with 10% H2SO4 resulted in an additional release of 30% of 137Cs from the organic-rich soil (range 30-35%) and 38% from the organic-poor soil horizon (range 27-53%). Extraction with 30% H2O2 released 11 and 15% of the 137Cs activity from organic-rich and organic-poor soil horizons. The corresponding values for treatment with 98.8% NaOCl were about 27% in both types of soil. About 11% of the total 137Cs activity was found in the humic acid fraction, about 5% in the fulvic fraction and 46% in the residue fraction. Relatively high level of 137Cs activity in soil (ca. 50%) was thus still left unsolved in the residue fraction. About 29% of 137Cs activity concentration in fungal mycelia was found as water soluble with a range of 11 to 41%. Additionally 24% of the 137Cs activity from mycelia was released by 1 M ammonium acetate extraction. Together, water and 1 M ammonium acetate extraction released about 53% of the total 137Cs activity in the mycelia. In fruit bodies of mycorrhizal fungi, 68% of the total 137Cs inventory was found to be water soluble at room temperature and 93% at 80 degrees C.     

Predictions of in situ solid/liquid distribution of radiocaesium in soils

Previous work has demonstrated that plant uptake of radiocaesium (RCs) is related to the activity concentration of RCs in soil solution, which is linked to the soil/soil solution distribution coefficient, K(D). The solid-liquid distribution of RCs is generally studied in soil suspensions in the laboratory and there are few reported measurements for in situ soil solutions. From a data set of 53 different soils (contaminated with either 134CsCl or 137CsCl) used in pot trials to investigate grass uptake of RCs, we analysed the variation of in situ K(D) with measured soil properties. The soils differed widely in % clay (0.5-58%), organic matter content (1.9-96%) and pH (2.4-7.0, CaCl2). The K(D) varied between 29 and 375,000 L kg-' (median 1460 L kg(-1)). Stepwise multiple regression analysis showed a significant correlation between the log K(D) and pH (p < 0.001), log %clay (p < 0.01) and log exchangeable K (p < 0.001) (overall R2 = 0.70). The in situ K(D) values were further compared to K(D)S predicted using an existing model, which assumes that RCs sorption occurs on specific sites and regular ion-exchange sites on the soil solid phase. Sorption of RCs on specific sites was quantified from the radiocaesium interception potential (RIP) measured for each soil and the soil solution concentrations of K+ and NH4+. The in situ log K(D) correlated well with the predicted K(D) (R2 = 0.85 before plant growth, R2 = 0.83 after plant growth). However, the observations were fivefold to eightfold higher than the predictions, particularly for the mineral soils. We attribute the under-prediction to the long contact times (minimum 4 weeks) between the RCs tracers and our experimental soils relative to the short (24 h) contact times used in RIP measurements. We conclude that our data confirmed the model but that ageing of RCs in soil is a factor that needs to be considered to better predict in situ KD values.     

Predicting the transfer of radiocaesium from organic soils to plants using soil characteristics

A model predicting plant uptake of radiocaesium based on soil characteristics is described. Three soil parameters required to determine radiocaesium bioavailability in soils are estimated in the model: the labile caesium distribution coefficient (kd1), K+ concentration in the soil solution [mK] and the soil solution-->plant radiocaesium concentration factor (CF, Bq kg-1 plant/Bq dm-3). These were determined as functions of soil clay content, exchangeable K+ status, pH, NH4+ concentration and organic matter content. The effect of time on radiocaesium fixation was described using a previously published double exponential equation, modified for the effect of soil organic matter as a non-fixing adsorbent. The model was parameterised using radiocaesium uptake data from two pot trials conducted separately using ryegrass (Lolium perenne) on mineral soils and bent grass (Agrostis capillaris) on organic soils. This resulted in a significant fit to the observed transfer factor (TF, Bq kg-1 plant/Bq kg-1 whole soil) (P < 0.001, n = 58) and soil solution K+ concentration (mK, mol dm-3) (P < 0.001, n = 58). Without further parameterisation the model was tested against independent radiocaesium uptake data for barley (n = 71) using a database of published and unpublished information covering contamination time periods of 1.2-10 years (transfer factors ranged from 0.001 to 0.1). The model accounted for 52% (n = 71, P < 0.001) of the observed variation in log transfer factor.     

The partitioning of sellafield-derived radiocaesium in scottish coastal sediments

Sequential leaching of Clyde Sea Area and Loch Etive sediments suggests that partitioning of Sellafield (formerly Windscale)-derived ¹³⁷Cs is related, to a larger than expected extent, to the concentration of sedimentary oxides, organics and, less importantly, carbonates. These components act to prevent ¹³⁷Cs release from clay mineral exchange sites. Leaching of wet sediments appears to provide quite different and presumably more realistic information on nuclide associations relative to that produced by leaching dry ground sediments. The latter ¹³⁷Cs partitioning data appear to overestimate the degree of ¹³⁷Cs fixation in these coastal deposits. Because of the observed partial association of ¹³⁷Cs with nonclay constituents, diagenetic remobilisation of the nuclide is in theory feasible and a preliminary study suggests its occurrence to a minor degree.     

The In vivo measurement of radiocaesium activity in lambs

Contamination of certain areas of the UK with radiocaesium from the Chernobyl accident led to restrictions being placed on the movement of lambs in these areas. To determine whether part of an area met the criteria for derestriction required the laboratory monitoring of meat from lambs sacrificed for the purpose. This was a slow process because there was no means of knowing which parts of an area had the lowest activity levels in lambs, that is where the chances of removing restrictions were the greatest. A rapid, simple and cheap method for the in vivo monitoring of caesium activity in lambs was developed. Correlation between the results from this method and in-laboratory measurements was reasonable (R² from 83% to 95%). The method was used successfully to monitor lambs in Cumbria and north Wales during July and August 1986.     

The influence of the sorptive properties of organic soils on the migration rate of 137Cs

Using a compartment model, the migration rates of 137Cs were calculated for two types of organic soils: a low peat-muck soil and a black earth. The migration rates of 137Cs in the tested soils turned out to be significantly higher than in mineral types examined earlier and ranged from 0.6 to 12.3 cm/year. The partition coefficients (Kd) were also determined for samples with varying organic matter content (OM) that were taken from different layers of the studied soils. The experimental results indicate that there is a clear relationship between Kd values and OM. The investigation was widened by microcalorimetric measurements which confirmed that the adsorption of 137Cs on the organic soils is low.     

Modelling the long-term dynamics of radiocaesium in closed lakes

During the years after the Chernobyl accident the radioceasium activity concentration in most contaminated aquatic ecosystems decreased markedly. Lakes with no permanent inflows and outflows (closed lakes), however, still present a radioecological problem which is expected to continue for some time. In this paper, a mechanistic model for the long-term prediction of radiocaesium behaviour in closed lakes is developed. The model of Prokhorov (Radiokhimiya (Radiochemistry) 11 (1969) 317) was modified to describe the effects of bottom sediment bioturbation, surface runoff from the catchment and suspended solids formation and sedimentation. The model input parameters are the effective diffusion coefficient in bottom sediments, depth of the completely mixed layer, the distribution coefficient in the sediment-water system, the runoff coefficient, sedimentation rate, and deposition density. Values of all these parameters can be independently estimated or measured in a short-term experiment. Given negligible runoff and sedimentation, the dynamics of radiocaesium in lake water is described by a simple equation with only one unknown parameter. This allows us to make long-term predictions on the basis of a series of measurements carried out during the relatively short period. The model was tested against 137Cs activity concentrations measured between 1993 and 1999 in Svyatoe lake in the Bryansk region of Russia. Calculated and measured activity concentrations are in good agreement.     

The effect of organic amendment on potential mobility and bioavailability of 137Cs and 60Co in tropical soils

In this work the role of organic matter in the potential mobility and bioavailability of 137Cs and 60Co in Brazilian soil was investigated. Radish was cultivated in pots containing the top layer (0-20 cm) of a Histosol, Ferralsol and Nitisol spiked with 137Cs and 60Co. In the case of the Ferralsol and Nitisol samples, besides the control, two different rates of organic amendments were used. In these soils, a sequential extraction protocol was used to identify the main soil compartments that could be responsible for the variation of transfer factor values. Our results indicate that organic amendment could be suggested as a practical countermeasure for 137Cs and 60Co contamination, since it reduces bioavailability of radionuclides and, consequently, soil to plant transfer factor values by almost one order of magnitude in a short period of time.     

Seasonal variation of the radiocaesium transfer soil-to-Swiss chard (Beta vulgaris var. cicla L.) in allophanic soils from the Lake Region, Chile

The transfer factor (TF) of radiocaesium from soil-to-Swiss chard (Beta vulgaris var. cicla L.) was studied in two different characteristic allophanic soils (umbric andosol and dystric fluvisol) of the Lake Region, an important agricultural region situated in central-south Chile. To investigate especially the time dependence and the effect of K-fertilisation on the TF, field experiments were conducted. Plots of 7.6 m2 were labelled with 100 kBq 134Cs m(-2) at Santa Rosa Experiment Station close to the city of Valdivia characterised by a temperate climate and high precipitation rates. The variation in time of the radiocaesium TF soil-to-Swiss chard was observed during two consecutive years after soil contamination by sequential harvests and radiocaesium analyses of the plants. The TFs showed no significant ageing effect, but a pronounced seasonal decrease with effective half-lives of about 140 and 160 days for the umbric andosol without and with K-fertilisation, respectively, and of 50 and 60 days for the dystric fluvisol without and with K-fertilisation, respectively. The effect of K-fertilisation on the absolute values of the TF was determined by the ratio between the median TF values obtained for corresponding dates without and with use of K-fertiliser. A ratio of TF(without K)/TF(with K) = 1.8 for the umbric andosol and TF(without K)/TF(with K) = 2.9 for the dystric fluvisol was obtained, indicating a reduction of the TF by applying 90 kg K ha(-1). The maximal values of the TF to chard predicted by the equation characterising the seasonal decrease of the TF at the beginning of the harvest periods are 0.19 for the umbric andosol and 0.11 for the dystric fluvisol, both values for soil treated with common K-fertilisation.     

Environmental study of fallout plutonium in soils from the piemonte region (North-West Italy)

The distributions of ²³⁸Pu and ^239+240Pu in surface soils from the Piemonte region were measured and the main factors influencing Pu concentrations investigated. Rainfall, altitude and the concentration of organic matter play an important role, while other soil parameters (pedology, lithology and geomorphology) are of lesser significance. Contour maps of the surface soil concentrations of ²³⁸Pu and ^239+240Pu are reported.     

Analysis of radiocaesium in the Lebanese soil one decade after the Chernobyl accident

Fallout from the Chernobyl reactor accident due to the transport of a radioactive cloud over Lebanon in the beginning of May 1986 was studied 12 years after the accident for determining the level of (137)Cs concentration in soil. Gamma spectroscopy measurements were performed by using coaxial high sensitivity HPGe detectors. More than 90 soil samples were collected from points uniformly distributed throughout the land of Lebanon in order to evaluate their radioactivity. The data obtained showed a relatively high (137)Cs activity per surface area contamination, up to 6545Bqm(-2) in the top soil layer 0-3cm. The average activity of (137)Cs in the top soil layer 0-3cm in depth was 59.7Bqkg(-1) dry soil ranging from 15 to 119Bqkg(-1) dry soil. The horizontal variability was found to be about 45% between the sampling sites. The depth distribution of total (137)Cs activity in soil showed an exponential decrease. Estimation of the annual effective dose due to external radiation from (137)Cs contaminated soil for selected sites gave values ranging from 19.3 to 91.6 micro Svy(-1).     

A rapid method for the In vivo monitoring of radiocaesium activity in sheep

Following the accident at Chernobyl there was a need to determine caesium activity in individual sheep on farms. This need arose so that animals on farms within a restricted area could be released from restrictions provided the tissue caesium activity was below the recommended limit. This paper describes the development of a rapid method for the in vivo monitoring of sheep using a lead-shielded sodium iodide scintillation detector coupled to a portable single channel analyser. The method enables one sheep per minute to be monitored and the results showed a good correlation (R² = 93%) with laboratory measurements of meat from sheep which had previously been monitored in vivo prior to sacrifice.     

Modelling the long-term behaviour of radiocaesium and radiostrontium in two Italian lakes

The present paper describes the application of a state-of-the-art model to two lakes in central Italy (Trasimeno and Monterosi) for the assessment of migration parameters of (137)Cs and (90)Sr (migration velocity to sediment, transfer rates from sediment to water and to bottom sediment). Applications of a compartment model and a model based on the diffusion equation to predict the behaviour of pollutants in water and through bottom sediment are presented and discussed. The application of the diffusion equation shows some difficulties of a general nature and typical of such a modelling approach. Moreover, there is no evidence of significant improvements of the model performances when the diffusion equation is applied. Very low levels of sedimentation rate of suspended matter in Lake Monterosi were evaluated by the quantitative assessment of radiocaesium migrating to bottom sediment. This suggests that, in this lake, the removal of radionuclide from the water column is mainly due to the turbulent mixing of bottom sediment causing radionuclide burial.     

The transfer of radiocaesium to ewes through a breeding cycle--an illustration of the pitfalls of the transfer coefficient

A study to measure the transfer of radiocaesium to adult female sheep through a breeding cycle is described. The transfer of radiocaesium from the diet to muscle (estimated as the equilibrium transfer coefficient) was significantly lower to pregnant, and especially lactating, animals compared to non-lactating and barren animals. High dry matter intake rates were also associated with significantly lower transfer coefficients. Known relationships between dry matter intake rates and protein turnover could credibly explain some of these differences. However, when described as the concentration ratio, radiocaesium transfer to meat was apparently highest during lactation. The apparent difference in results obtained by the two approaches of determining transfer is the consequence of daily dry matter intake being a denominator within the estimation of transfer coefficient. A wider discussion of transfer coefficients and concentration ratios leads us to suggest that the concentration ratio is the more robust and potentially generic parameter.     

Uptake and elimination of radiocaesium in fish and the "size effect."

A number of hypotheses have previously been developed concerning the rates of uptake and elimination of radiocaesium (137Cs) in fish. These include the influence of potassium and other water chemical parameters on both uptake and elimination, and the effect of fish size on accumulation. In order to test these hypotheses, we have assembled a data set comprising more than 1,000 measurements of radiocaesium (137Cs) in predatory fish (perch, pike and brown trout) in nine European lakes during the years after Chernobyl. These data have been analysed using simple models for uptake and excretion of 137Cs in fish, showing that: 1. Fish-water concentration factors (CF) were inversely proportional to potassium [K+] concentration of the different lakes, in agreement with previous studies. 2. The uptake rate of 137Cs in fish was negatively correlated with lake [K+], but excretion rate was independent of [K+]. 3. Lower than expected CF values were found in one lake, Iso Valkj?rvi, Finland. This is attributed to inhibition of the K+ (and therefore 137Cs) high affinity transport system in aquatic plants and fish by low pH and/or low Ca2+. 4. The inclusion of fish weight as a parameter in our dynamic model significantly improves the ability of the model to fit the observed measurements of 137Cs. 5. The model developed from the above hypotheses was able to fit the data from nine different lakes to within approximately a factor of 3 of the observed values.     

The true distribution and accumulation of radiocaesium in stem of Scots pine (Pinus sylvestris L.)

The radial and vertical distributions of radiocaesium, potassium and calcium were determined in two Scots pine stands (17 and 58 yr old) similarly affected by the Chernobyl fallout. For both age classes, concentrations are always the lowest in the stemwood, highest in the inner bark and intermediary levels were observed for the outer bark. Due to the cumulative character of its biomass. however. stemwood is a long-term major reservoir of 137Cs. With tree development, changes in the 137Cs radial distribution are well described by variations in the sap ascent pattern and reveal an important transfer between tree rings. It is shown that. both the biomass evolution and knowledge of the evolution of the 137Cs radial gradient are important to predicting 137Cs accumulation in wood with time. According to the common transfer factor (TF) approach, one would expect a decrease in radiocaesium accumulation with time (from 0.0047 +/- 0.0013 to 0.0035 +/- 0.0008 m2kg(-1) for the 17 and 58 yr old trees, respectively). With the wood immobilisation potential (WIP) approach, it was, however, clearly shown that additional annual uptake was highest for the older stand (3.12 +/- 0.23 Bq cm(-3) yr(-1) for the 58-year-old stand compared to 1.99 +/- 0.30 Bq cm(-3) yr(-1) for the younger stand). Following the WIP approach, it was moreover possible to distinguish between the 137Cs incorporated via the root uptake process and a possible lasting effect of interception. It is shown that, whereas for the younger stand (5 yr old at the time of the accident) root uptake contributed exclusively to the wood contamination, the former process explained only 48% of the measured total 137Cs content in the wood of the older tree.     

Levels of PCDD/Fs and trace elements in superficial soils of Pavia Province (Italy)

Trace elements and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in soils from rural and light-industrialized sites (n=168) of Province of Pavia (Northern Italy). Most of the trace element values fit in typical ranges of concentrations in soils and are similar to the ones reported for rural sites in Italy or sites with no direct anthropogenic impact. Total concentrations of 2,3,7,8 chlorine substituted PCDD/Fs in superficial soils ranged between 24.4 and 1287 pg g(-1) dw (0.5-28.9 pg WHO(98)-TEQ g(-1) dw). The North Eastern part of the Province presented significantly higher levels (p<0.001) than the rest of the Province for As, Cd, Hg, Pb, Zn and PCDD/Fs. While the existence of a defined heavy metal polluting source for this specific site has been suggested, in the case of PCDD/Fs, profiles were not linked to any specific emission source fingerprint. In the whole extension of Pavia Province, OCDD/F dominated the 2,3,7,8 chlorine substituted congener soil pattern, followed by the 1,2,3,4,6,7,8 hepta-CDD/F congener. Principal Component Analysis (PCA) showed that this profile could not be associated to any described PCDD/F emission source fingerprint and was relatively similar to the baseline deposition of sites with no direct impact of PCDD/F emission sources independently of land use.     

Long-term investigations of radiocaesium activity concentrations in carp in North Croatia after the Chernobyl accident

Long-term investigations of radiocaesium activity concentrations in carp in the Republic of Croatia are presented. The radiocaesium levels in carp decreased exponentially and the effective ecological half-life of (137)Cs was estimated to be about 1 year during 1987-2002 and 5 years during 1993-2005. The observed (134)Cs:(137)Cs activity ratio in carp was found to be similar to the ratio observed in other environmental samples. The concentration factor for carp (wet weight) was estimated to be 128+/-74 Lkg(-1), which is in reasonable agreement with model prediction based on K(+) concentrations in water. Estimated annual effective dose received by adult members of the Croatian population due to consumption of carp contaminated with (134)Cs and (137)Cs are small: per capita dose from this source during 1987-2005 was estimated to be 0.5+/-0.2 microSv. Due to minor freshwater fish consumption in Croatia and low radiocaesium activity concentrations in carp, it can be concluded that carp consumption was not a critical pathway for the transfer of radiocaesium from fallout to humans after the Chernobyl accident.